Photographic processing for photographic silver halide light-sensitive elements

ABSTRACT

In photographic processings for photographic silver halide light-sensitive elements which include a prehardening step and development step, an improvement which comprises processing the light-sensitive element between the prehardening step and the development step in an aqueous solution containing a resorcinol derivative represented by the following general formula:   The moieties A and B are defined in the specification.

United States Patent Iwano et al.

[54] PHOTOGRAPHIC PROCESSING FOR PHOTOGRAPHIC SILVER HALIDELIGHT-SENSITIVE ELEMENTS [72] Inventors: Haruhiko lwano; lsao Shimamura,both of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,Kanagawa,

Japan [22] Filed: Oct. 4,1968

21 Appl. No.: 765,032

[30] Foreign Application Priority Data Oct. 4, 1967 Japan ..42/63936[52] US. Cl. ..96/66.5, 96/50 PT, 96/109, 96/111 [51] Int. Cl ..G03c5/30 [58] Field of Search ..96/66.5, 109, 22, 50, 50 PT, 96/111;260/621, 623, 625, 456, 473, 512, 521, 556, 559, 613

[56] References Cited UNITED STATES PATENTS 2,165,421 7/1939 Sheppard eta1. 96/l11 2,586,168 2/1952 Kaszuba ..96/l09 X Mar. 14, 1972 FOREIGNPATENTS OR APPLICATIONS 504,378 4/1939 Great Britain ..96/l09 PrimaryExaminer-William D. Martin Assistant Examiner-M. R. LusignanAttorney-Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT Inphotographic processings for photographic silver halide light-sensitiveelements which include a prehardening step and development step, animprovement which comprises processing the light-sensitive elementbetween the prehardening step and the development step in an aqueoussolution containing a resorcinol derivative represented by the followinggeneral formula:

T e msiss sw n B are lnihg ssi s gi 4 Claims, No Drawings PHOTOGRAPHICPROCESSING FOR PI-IOTOGRAPHIC SILVER HALIDE LIGHT-SENSITIVE ELEMENTSBACKGROUND OF THE INVENTION 1. Field of the Invention The presentinvention relates generally to photographic processing for photographicsilver halide light-sensitive elements, and more particularly to aprocess for reducing the formation of fogs occurring during hardeningsilver halide emulsion layers.

2. Description of the Prior Art In general, when photographiclight-sensitive films, photographic printing papers or photographiclight-sensitive plates having silver halides are processed afterexposure, they are frequently subjected to hardening processing prior todevelopment.

The object of the hardening process is to prevent emulsion layers frombeing mechanically damaged during processing by increasing themechanical strength of the emulsion layers of photographic silver halidelight-sensitive elements, and in particular, the application of thehardening processing is quite effective when the mechanical strength ofthe photographic emulsion layers is originally insufficient, thephotographic emulsion layers are processed for a long period of time, orthey are processed in a processing solution having a high pH or a hightemperature.

The hardening processing conducted before the development step isusually called prehardening," and as a hardening agent for theprocessing, there is usually employed an aldehyde capable of hardeninggelatin in the photographic emulsion layer by reaction therewith, suchas formaldehyde, glyoxal, succinicaldehyde, glutaraldehyde, and thelike.

Although the photographic emulsion layers are effectively hardened bythis kind of prehardening processing, it has a bad influence on thephotographic properties of the photographic emulsion layers thusprocessed, for example, the formation of development fogs is increased,the development density at reversal development is reduced, and thecoupling property of couplers in photographic light-sensitive colorelements is varied.

SUMMARY OF THE INVENTION A and B each represent a member selected fromthe group consisting of a hydrogen atom, a lower alkyl group, a halogenatom, OR (wherein R, is a lower alkyl group), ZOR (wherein R is a memberselected from the group consisting of a hydroxyl group, an alkoxylgroup, and NH and SO R (wherein R is a member selected from the groupconsisting of a hydroxyl "group, an alkoxyl group, and NH Therefore, anobject of the present invention is to provide an improved photographicprocessing for photographic lightsensitive elements capable of providingsufficient mechanical strength to the emulsion layers of saidphotographic light-sensitive elements, which is not accompanied by the.aforesaid drawbacks.

DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the presentinvention, an improved photographic processing for photographiclight-sensitive elements is provided in which the photographiclight-sensitive elements are processed between a prehardening step and adevelopment step in an aqueous solution containing a resorcinolderivative represented by the general formula wherein A and B eachrepresent a hydrogen atom, a lower alkyl group, a halogen atom, OR(wherein R represents a lower alkyl group), COR (wherein R represents ahydroxyl group, an alkoxyl group, or NH;) or SO R (wherein R representsa hydroxyl group, an alkoxyl group, or Nl-l Typical examples of theabove resorcinol derivative are resorcin, 4-chlororesorcin,4,6-dichlororesorcin, 4-methoxyresorcin, 4-methylresorcin, and4-carboxyresorcin.

The concentration of the resorcinol derivative depends upon theconcentration of the aldehyde coming from the prehardening processing,but the aldehyde from the prehardening processing can generally beeffectively removed at a concentration range of 0. 1-100 g./liter of theresorcinol derivative.

The aqueous solution for the antifogging processing may be used at anypH range, but is particularly effective in a neutral state or an acidstate. Moreover, the aqueous solution containing the resorcinolderivative may contain pH-controlling agents or buffering agents, suchas sodium sulfate, borax, acetic acid, sodium acetate, sodium carbonate,sulfuric acid, and boric acid, as well as other conventionalantifoggants such as an alkali halide.

The photographic emulsion layer to be processed according to the processof this invention contains, as the light sensitive material,conventional silver halides. As the dispersoid for the light-sensitivematerial, there is generally employed gelatin or a mixture of gelatinand another hydrophilic high molecular weight material. As a support forthe photographic emulsion layer, there may be employed a glass plate, acellulose ester film, a polyester film, a paper, and the like.

The process of this invention is particularly suitable when applied toprocessing reversal color photographic light-sensitive elements whichare desirably processed at a high pH and for a long period of time; andalso for processing color photographic printing papers which arepreferably quickly processed at a high temperature.

In the practice of the process of this invention, the formation ofdevelopment fogs is low; when compared with a conventional photographicprocessing. In addition, a reduction in development density does notoccur and the coupling property of couplers in color photographiclight-sensitive elements is not varied.

The invention will be further explained in detail by the followingexamples, although the invention shall not be limited to them.

EXAMPLE 1 A panchromatic gelatino silver iodobromide emulsion layersufficiently color sensitized (formed on a cellulose acetate film) wasexposed by means of a sensitometer and subjected to the followingphotographic processings at 40 C.

Processing Time Frehardening 35 sec. Washing 10 sec. Antifoggingprocessing 45 sec. Washing 20 sec. Development 50 sec, Stopping 10 sec,Fixing 30 sec.

Washing 90 sec.

The compositions for the processing solutions used in the aboveprocessings are as follows:

Prehardening composition Sodium bisulfite l g. Formalin (37% aq. soln.)l ml. Borax 5 g, Sodium sulfate 50 g. Potassium bromide 2 g.

Water to make Antifogging composition The resorcinol derivative shown inthe following table was added to one liter of an aqueous solutioncontaining 5 g. of glacial acetic acid and 4 g. of sodium acetate.

Water to make I l.

The photographic properties of the test films processed as describedabove are shown in Table 1.

TABLE 1 Test No. Fog Relative sensitivity Gamma value 1 (control) 0.362.20 0.32 2 0.27 2.30 0.33 3 0.25 1.31 0.33 4 0.26 2.32 0.35 5 0.23 2.320.36

In Table 1, the relative sensitivity is shown by the logarithmic valueof the reciprocal of the exposure amount corresponding to the blackeneddensity of0.l over fog.

It is clear from the above results that by the application of theantifogging processing of this invention, the formation of developmentfog was effectively prevented and the sensitivity, as well as the gammavalue, were increased.

Also, by the application of the antifogging bath, the prehardeningprocess can be practically employed to improve the mechanical strengthof the emulsion layers. Thus, the lightsensitive elements may beprocessed at a high temperature without being accompanied by operativetroubles.

EXAMPLE 2 A panchromatic gelatino silver halide emulsion layersufiiciently color sensitized and formed on a polyester film was exposedby means of a sensitometer through a silver step wedge and thensubjected to the following photographic processings at 27 C. (exceptdrying which was conducted at 38 C.).

Processing Time Prehardening 60 sec. Washing 30 sec. Antifoggingprocessing 60 sec. Washing 30 sec. Primary development 210 sec. Washing30 sec. Bleaching sec. Washing 30 sec. Cleaning 60 sec. Washing 30 sec.Secondary development 120 sec. Washing 30 sec. Fixing 90 sec. WashingISO sec. Drying sec.

The compositions for the above processings are as follows:

Prehardening composition Same as in Example 1.

Antifogging composition The resorcinol derivative shown in the followingtable was added to one liter of an aqueous solution containing 4 g. ofsodium acetate, 5 ml. of glacial acetic acid, and 0.7 g. of potassiumbromide.

Primary and secondary developers 0.8 g./liter of potassium thiocyanatewas added to the developer in Example 1.

Bleaching solution Sulfuric acid 5 ml.

Potassium bichromate 4 g. Water to make l l. Cleaning composition Sodiumsulfite 50 g.

Water to make Fixing solution Same as in Example I.

Results of the above processing are shown in the following table.

TABLE 2 Test No. Additives Reversal density l (control) none L12 24-Chlororcs0rcinol 2 g. l .43 3 d-Chlororesorcinol S g. l .46 44-Chlororesorcinol 10 g. l .48

It is clear from the above results that the reversal density wasincreased by using the antifogging bath according to the process of thisinvention; hence, better photographic properties were obtained in thephotographic film thus processed in spite of the appiication of theprehardening processing. Moreover, during the processing of thisinvention, the surface of the emulsion layer was less damagedmechanically, and the drying load could be reduced.

EXAMPLE 3 A multiple layer photographic color film prepared by applyingto a cellulose acetate film a gelatino silver iodobromide emulsionhaving a red sensitivity, a gelatino silver iodo-bromide emulsion havinga green sensitivity, a yellow filter layer containing fine colloidalsilver particles and having a blue-absorptive property, and a gelatinosilver iodobromide emulsion having a blue sensitivity (in this order)was exposed through a silver step wedge by means of a sensitiometer andthen subjected to the following photographic processings at 24 C.

Processing Time Prehardening W ashin g Antifogging processing WashingPrimary development Washing l min.

1 min.

1 min.

1 min.

min.

2 min.

Reversal exposure at 200 CMS (red light) from the back side of the film.

Cyan color development Washing Reversal exposure (blue light) at 200 CMSfrom the emulsion side of the film.

Yellow color development W ashing Secondary development W ashingReversal exposure (white light) at 2000 CMS. from the opposite sides ofthe film.

Magenta color development Washing Bleaching Washing Fixing Washing Thecompositions for the above processings were as follows:

Prehardening composition Same as in Example 1. Antifogging compositionThe resorcinol derivative shown in the following table was added to oneliter of an aqueous solution containing 8 g. of boric acid, 0.3 ml.ofsulfuric acid, and 0.8 g. of potassium bromide to rovide theantifogging bath.

5 min.

2 min.

5 min.

1 min.

1 min.

1 min.

5 min.

5 min.

2 min.

1 min.

2 min.

2 min.

Test No. Additive Amount 1 (control) none 2 Resorcin 5 g. 3 Resorcin g.4 4-Chlororesorcin 5 g. 5 d-chlororesorcin 10 g.

Primary and secondary black and white developers Same as in Example 2.

Cyan color developer Sodium sulfite 5.0 g.2-Arnino-5-dielhylaminotoluene sulfate 06 g. Sodium carbonatemonohydrate15.0 g. Potassium bromide 0.5 g. Potassium iodide (0.11 aq.so1n.) 5 ml.1.5-Dihydroxy-2.6 dibromonaphthalene 1.2 g. Sodium hydroxide 2.0 g.Water to make 1 1.

Yellow color developer Sodium sulfite 5.0 g.N,N-Diethyl-p-phenylenediamine 2.5 g. sulfite Potassium bromide 1.0 g.Potassium iodide (0.1% aq. soln.) 5.0 ml. mBenzoyl-4-(p-toluenesulfoamido)- 1.2 g. acetanilide sodium hydroxide 2.5g. Water to make 1 l. Magenta color developer Sodium sulfite 5.0 g.2-Amino-S-diethylaminotoluene 2.0 g. hydrochloride Potassium bromide 0.8g.

It is clear from the above table that the coupling density wasremarkably increased by employing the antifogging processing accordingto the process of this invention, and no harmful influence on thephotographic properties were observed, that is, contamination andsensitivity reduction were not observed.

EXAMPLE 4 A commercially available photographic color printing paper wasexposed by means of a sensitometer and processed as follows at 20 C.

Processing 1 Time Color development 5 min. Washing 5 min. Bleach-fixing8 min. Washing 10 min. Hardening 5 min. Washing 5 min. Bufferingprocessing 5 min. Washing 5 min. Stabilization 5 min.

Drying (at 38 C.).

The compositions used for the processings were as follows:

Color developer N-Ethyl-N-hydroxyethyl-p-phenylenediamine sulfate 7.5 g.

Hydroxylamine sulfate 0.3 g.

Potassium carbonate 100.0 g.

Potassium bromide 1.0 g.

Sodium sulfite (anhydrous) 4.5 g.

Sodium tripolyphosphate 1.0 g.

Water to make 1 1. Bleach-fixing composition lron salt ofethylenediaminetetracetic acid 500 g.

Sodium carbonate (anhydrous) 2.5 g.

sodium sulfite (anhydrous) 10.0 g.

Sodium thiosulfate (anhydrous) 200.0 g.

Water to make 1 l Hardening composition Tetrasodium slat ofethylenediamine-tetracetic acid 0.5 g.

Sodium carbonate 10.0 g.

Sodium sulfate 50.0 g.

Formalin (37% soln.)

Sodium bisulfite 4.0 g. TABLE 4 Water to make l l. Buffering solutionProcessing Fog Density Red Density Green Density Blue Density Tartaricacid l0.0 g. 5 E08 L Ill 0.35 0.20 0.45 Water to make 1 l. I O 09 o 09 0Stabilization composition EXAMPLE x 'fsf ig gg f 40g 10 A geiatinosilver halide emulsion layer having a red sen- Sodium dihydrogeriphosphate sitivity formed on a cellulose acetate film was exposedthrough Disodiurri hydrogen phosphate 2.0 g. a silver step wedge bymeans of a sensitometer and subjected to the following reversal colorprocessing, at 24 C. diamine-teiraacetic acid 1 .0

Water to make 1 1.

Processing Time By the practice of Processing 1, good photographicqualities in the photographic print were obtained, but it was accom-Prehardening 60 sec, panied by one fault, i.e., the printing paper hadto be i 2g processed for a longer period of time (as shown above). agzsg 60 Therefore, to shorten the processing time, the printing primarydevelopment 210, paper was processed at 35 C. (Processing II). In thiscase, a Washing 60 my so-called reticulation" formed on the emulsionlayer, which reduced the commercial value of the printing paper.

A hardening procedure was then conducted before the 25 Reversal BXPOSUIEat 2 MS- m r hi light. color development (Processing ll). That is,instead of the hardening procedure, in Processing 1, the printing paperwas Cyan color development 210 sec. processed for 60 seconds beforecolor development in a 60 Bleaching 60 sec. hardening bath having thefollowing composition: washing 60 sec Fixing so sec. Washing 60 sec.

Hmdmmg The compositions of the prehardening bath and the antifoggingbath used were the same as in Example 1, the other Fvrmalifl 1- -l 20 M35 compositions being the same as in Example 3. The results are2,5-Dimethoxyteirahydrofuran 4 ml. w Sulfuric Acid 2 m1 sho n in thefollowing table.

Sodium sulfate [00 g. Potassium bromide 2 g. TABLE 5 Borax 5 g. I winerto make I I Test No. Additive Amount Reversal Density (red density) 1(control) none 0.55 2 Resorcin 5 g. L01

By the practice of Processing Ill, intense development fogs 3 i 5 8- r dlth h th in cha ical tre til i the emulsion 5 orme oug e e n 5 g o 54-Methoxyresorcin S g. L05 layer was improved. Hence, the commercialvalue of the pnnt- 6 d-Methylresorcin s g. i.o4 ing paper wasnonetheless lost (as in Processing 1!).

Accordingly, Processing IV of this invention employing the It is clearfrom the above results that by the use of the anantifogging processingwas conducted, and by this procedure tifogging bath, coupling densitywas remarkably increased. better photographic qualities as in Processing1 were obtained.

Moreover, the printing paper could be processed in a short EXAMPLE 6Period 9 as Show f mamtammg 'f A reversal magenta color development wasconducted basimechanical strength of the light-sensitive emulsion layer.This u as in Example Specifically the procedure of Exampe O I QProcessmg was conducted at 38 5 was repeated employing the magenta colordeveloper shown in Example 3 instead of the cyan color developer ofExample 5, and an antifogging composition as shown in the followingprocessing 1v Time table was instead employed. The antifogging bath wasin aqueous solution containing 50 gJIiter of sodium sulfate, 5.0Hardening s g./liter ofsodium brsulfite, 1.0 g. ofbonc acid, and 0.5g./l1ter Washing 30 sec. of potassium bromide, together with thefollowing resorcin Antifogging processing 60 sec. derivative Washing 30sec. Color development I00 sec. V washing 30 Test No. Additive Amount(g.ll.) Bleach-fixing 140 i; 1 (control) none Washing 30 sec. 2 Resmcm 5Buffering 40 sec 3 -chlororesorcin 5 Washing 30 sec 44.6-Dtchlororesorcin 5 Stabilization 40 sec. 5 Mflhwywwfcm 5 Drying (atC) 6 d-Methylresorcin 5.

Results are shown in the following table.

The antifogging bath used in the process was an aqueous 7 TABLE 6solution containing 10 g./liter of 4-chlororesorcin and 0.5 gJliter ofpotassium bromide. The hardening bath was the Test No. Reversal dens ity(green density) same as in Processing ill.

The fog densities of the printing papers processed by 3 1 42 ProcessingsI, ll, ill, and [V are shown in the following table. 4 2.40

As shown in the above table, the coupling density was markedly increasedby employing the antifogging processing of 5 wherein A and B eachrepresents a member selected from the group consisting of a hydrogenatom, a lower alkyl group, a halogen atom, OR wherein R is a lower alkylgroup, COR wherein R is a member selected from the group consisting of ahydroxyl group, an alkoxyl group, and NH2, and SO R wherein R is amember selected from the group consisting of a hydroxyl group, analkoxyl group, and NH 2. The photographic processing as claimed in claim1 wherein said resorcinol derivative is selected from the groupconsisting of resorcin, 4-chlororesorcin, 4,6-dichlororesorcin,4-methoxyresorcin, 4-methylresorcin, and 4-carboxyresorcin.

3. A photographic processing as claimed in claim 1 wherein saidphotographic silver halide light-sensitive element comprises a silverhalide and a mixture of gelatin with another hydrophilic high molecularweight material.

4. The photographic processing as claimed in claim 1 wherein saidaldehyde is selected from the group consisting of formaldehyde, glyoxal,succinicaldehyde and glutaraldehyde.

2. The photographic processing as claimed in claim 1 wherein saidresorcinol derivative is selected from the group consisting of resorcin,4-chlororesorcin, 4,6-dichlororesorcin, 4-methoxyresorcin,4-methylresorcin, and 4-carboxyresorcin.
 3. A photographic processing asclaimed in claim 1 wherein said photographic silver halidelight-sensitive element comprises a silver halide and a mixture ofgelatin with another hydrophilic high molecular weight material.
 4. Thephotographic processing as claimed in claim 1 wherein said aldehyde isselected from the group consisting of formaldehyde, glyoxal,succinicaldehyde and glutaraldehyde.